U.S. patent number 11,393,676 [Application Number 16/499,215] was granted by the patent office on 2022-07-19 for composition for depositing silicon-containing thin film containing bis(aminosilyl)alkylamine compound and method for manufacturing silicon-containing thin film using the same.
This patent grant is currently assigned to DNF CO., LTD.. The grantee listed for this patent is DNF CO., LTD.. Invention is credited to Se Jin Jang, Myong Woon Kim, Sung Gi Kim, Sam Dong Lee, Sang-Do Lee, Sang Ick Lee, Jeong Joo Park, Joong Jin Park, Byeong-Il Yang.
United States Patent |
11,393,676 |
Kim , et al. |
July 19, 2022 |
Composition for depositing silicon-containing thin film containing
bis(aminosilyl)alkylamine compound and method for manufacturing
silicon-containing thin film using the same
Abstract
Provided are a composition for depositing a silicon-containing
thin film containing a bis(aminosilyl)alkylamine compound and a
method for manufacturing a silicon-containing thin film using the
same, and more particularly, a composition for depositing a
silicon-containing thin film, containing the
bis(aminosilyl)alkylamine compound capable of being usefully used
as a precursor of the silicon-containing thin film, and a method
for manufacturing a silicon-containing thin film using the
same.
Inventors: |
Kim; Sung Gi (Daejeon,
KR), Park; Jeong Joo (Daejeon, KR), Park;
Joong Jin (Daejeon, KR), Jang; Se Jin (Jeju-si,
KR), Yang; Byeong-Il (Daejeon, KR), Lee;
Sang-Do (Daejeon, KR), Lee; Sam Dong (Daejeon,
KR), Lee; Sang Ick (Daejeon, KR), Kim;
Myong Woon (Daejeon, KR) |
Applicant: |
Name |
City |
State |
Country |
Type |
DNF CO., LTD. |
Daejeon |
N/A |
KR |
|
|
Assignee: |
DNF CO., LTD. (Daejeon,
KR)
|
Family
ID: |
1000006440897 |
Appl.
No.: |
16/499,215 |
Filed: |
March 28, 2018 |
PCT
Filed: |
March 28, 2018 |
PCT No.: |
PCT/KR2018/003655 |
371(c)(1),(2),(4) Date: |
September 27, 2019 |
PCT
Pub. No.: |
WO2018/182309 |
PCT
Pub. Date: |
October 04, 2018 |
Prior Publication Data
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|
|
Document
Identifier |
Publication Date |
|
US 20200111664 A1 |
Apr 9, 2020 |
|
Foreign Application Priority Data
|
|
|
|
|
Mar 29, 2017 [KR] |
|
|
10-2017-0040078 |
Apr 28, 2017 [KR] |
|
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10-2017-0055632 |
Mar 27, 2018 [KR] |
|
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10-2018-0035010 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C23C
16/308 (20130101); C23C 16/50 (20130101); H01L
21/02164 (20130101); C07F 7/10 (20130101); C23C
16/401 (20130101); C01B 33/183 (20130101); H01L
21/02271 (20130101); C23C 16/325 (20130101); H01L
21/02167 (20130101); C23C 16/345 (20130101); C01B
21/068 (20130101); C09D 1/00 (20130101); H01L
21/02208 (20130101); H01L 21/0217 (20130101); H01L
21/02126 (20130101); H01L 21/02274 (20130101); H01L
21/0228 (20130101); C23C 16/4554 (20130101); H01L
21/0214 (20130101); C23C 16/36 (20130101) |
Current International
Class: |
H01L
21/31 (20060101); C01B 21/068 (20060101); C07F
7/10 (20060101); C23C 16/455 (20060101); C23C
16/50 (20060101); C23C 16/40 (20060101); C23C
16/34 (20060101); C23C 16/30 (20060101); C23C
16/36 (20060101); C09D 1/00 (20060101); C23C
16/32 (20060101); C01B 33/18 (20060101); H01L
21/02 (20060101) |
Field of
Search: |
;438/778 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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103401019 |
|
Nov 2013 |
|
CN |
|
105377860 |
|
Mar 2016 |
|
CN |
|
2669249 |
|
Dec 2013 |
|
EP |
|
2008074847 |
|
Apr 2008 |
|
JP |
|
2014523638 |
|
Sep 2014 |
|
JP |
|
2014237644 |
|
Dec 2014 |
|
JP |
|
20140143682 |
|
Dec 2014 |
|
KR |
|
WO-2008038255 |
|
Apr 2008 |
|
WO |
|
2014196827 |
|
Dec 2014 |
|
WO |
|
2016049154 |
|
Mar 2016 |
|
WO |
|
Other References
Freza, S. et al., "Influence of substituents in vinyl groups on
reactivity of parylene during polymerization process," Chemical
Physics, vol. 368, No. 3, Mar. 11, 2010, Available Online Jan. 28,
2010, 7 pages. cited by applicant .
ISA Korean Intellectual Property Office, International Search
Report Issued in Application No. PCT/KR2018/003655, dated Jul. 13,
2018, WIPO, 2 pages. cited by applicant .
State Intellectual Property Office of the People's Republic of
China, Office Action and Search Report Issued in Application No.
201880019422.X, dated Nov. 13, 2020, 13 pages. (Submitted with
Partial Translation). cited by applicant .
Japanese Patent Office, Office Action Issued in Application No.
2019-553053, dated Nov. 27, 2020, 9 pages. cited by applicant .
United States Patent and Trademark Office, Office Action Issued in
U.S. Appl. No. 16/499,196, dated May 24, 2021, 19 pages. cited by
applicant .
"CAS No. 23636-57-9," ichemistry Website, Available Online at
http://www.ichemistry.cn/chemistry/23636-57-9.htm. Retrieved on
Dec. 1, 2021, 3 pages. (See NPL 1, Office Action Issued in U.S.
Appl. No. 16/499,196 for Explanation of Relevancy). cited by
applicant.
|
Primary Examiner: Kebede; Brook
Attorney, Agent or Firm: McCoy Russell LLP
Claims
The invention claimed is:
1. A composition for depositing a silicon-containing thin film, the
composition comprising a bis(aminosilyl)alkylamine compound
represented by the following Chemical Formula 1 is represented by
the following Chemical Formula 4 or 5: ##STR00020## in Chemical
Formula 1, R is C1-C7 alkyl or C2-C7 alkenyl; R.sub.1 to R.sub.4
are each independently hydrogen, C1-C7 alkyl, or C2-C7 alkenyl, or
R.sub.1 and R.sub.2, and R.sub.3 and R.sub.4 are each independently
linked to each other to form a ring; and R.sub.5 to R.sub.8 are
each independently hydrogen, halogen, C1-C7 alkyl, or C2-C7
alkenyl; ##STR00021## in Chemical Formulas 4 and 5, R is C1-C7
alkyl or C2-C7 alkenyl; R.sub.11 to R.sub.14 are each independently
hydrogen, C1-C7 alkyl, or C2-C7 alkenyl; R.sub.5 and R.sub.6 are
each independently C1-C7 alkyl, or C2-C7 alkenyl; and n and m are
each independently an integer of 1 to 7.
2. The composition of claim 1, wherein in Chemical Formulas 4 and
5, R is C1-C5 alkyl; R.sub.5 and R.sub.6 are each independently
C1-C5alkyl; and n and m are each independently an integer of 1 to
4.
3. The composition of claim 1, wherein the
bis(aminosilyl)alkylamine compound is selected from the following
compounds: ##STR00022##
4. A method for manufacturing a silicon-containing thin film, using
a composition for depositing the silicon-containing thin film,
wherein the method comprises a) maintaining a temperature of a
substrate mounted in a chamber at 30.degree. C. to 500.degree. C.;
b) contacting the composition with the substrate to adsorb the
composition in the substrate; and c) injecting a reaction gas into
the substrate in which the composition is adsorbed to the
silicon-containing thin film; wherein the composition comprising a
bis(aminosilyl)alkylamine compound represented by the following
Chemical Formula 1: ##STR00023## in Chemical Formula 1, R is C1-C7
alkyl or C2-C7 alkenyl; R.sub.1 to R.sub.4 are each independently
hydrogen, C1-C7 alkyl, or C2-C7 alkenyl, or R.sub.1 and R.sub.2,
and R.sub.3 and R.sub.4 are each independently linked to each other
to form a ring; and R.sub.5 to R.sub.8 are each independently
hydrogen, halogen, C1-C7 alkyl, or C2-C7 alkenyl.
5. The method of claim 4, wherein deposition is performed by an
atomic layer deposition method, a chemical vapor deposition method,
a metal-organic chemical vapor deposition method, a low-pressure
chemical vapor deposition method, a plasma-enhanced chemical vapor
deposition method, or a plasma-enhanced atomic layer deposition
method.
6. The method of claim 4, wherein the silicon-containing thin film
is a silicon oxide film, a silicon oxy carbide film, a silicon
nitride film, a silicon oxy nitride film, a silicon carbonitride
film, or a silicon carbide film.
7. The method of claim 4, wherein the reaction gas is supplied
after being activated by generating plasma with a plasma power of
50 to 1000 W.
8. The method of claim 4, wherein in Chemical Formula 1, R.sub.5 to
R.sub.7 are each independently hydrogen, halogen, C1-C7 alkyl, or
C2-C7 alkenyl, and R.sub.8 is hydrogen.
9. The method of claim 4, wherein the bis(aminosilyl)alkylamine
compound represented by Chemical Formula 1 is represented by the
following Chemical Formula 2 or 3: ##STR00024## in Chemical Formula
2 or 3, R is C1-C7 alkyl or C2-C7 alkenyl; R.sub.5 to R.sub.7 are
each independently hydrogen, halogen, C1-C7 alkyl, or
C2-C7-alkenyl; R.sub.11 to R.sub.14 are each independently
hydrogen, C1-C5 alkyl, or C2-C5 alkenyl; and n and m are each
independently an integer of 1 to 7.
10. The method of claim 9, wherein in Chemical Formula 2 or 3,
R.sub.5 to R.sub.7 are each independently hydrogen or C1-C7 alkyl;
R.sub.11 to R.sub.14 are each independently hydrogen, C1-C5 alkyl,
or C2-C5 alkenyl; and n and m are each independently an integer of
1 to 4.
11. The method of claim 4, wherein the bis(aminosilyl)alkylamine
compound represented by Chemical Formula 1 is represented by the
following Chemical Formula 4 or 5: ##STR00025## in Chemical
Formulas 4 and 5, R is C1-C7 alkyl or C2-C7 alkenyl; R.sub.11 to
R.sub.14 are each independently hydrogen, C1-C7 alkyl, or C2-C7
alkenyl; R.sub.5 and R.sub.6 are each independently C1-C7 alkyl or
C2-C7 alkenyl; and n and m are each independently an integer of 1
to 7.
12. The method of claim 4, wherein the bis(aminosilyl)alkylamine
compound represented by following Chemical Formula 1 is selected
from the following compounds: ##STR00026## ##STR00027##
13. A bis(aminosilyl)alkylamine compound represented by the
following Chemical Formula 1: ##STR00028## in Chemical Formula 1, R
is C1-C7 alkyl or C2-C7 alkenyl; R.sub.1 to R.sub.4 are each
independently hydrogen, C1-C7 alkyl, or C2-C7 alkenyl, or R.sub.1
and R.sub.2, and R.sub.3 and R.sub.4 are each independently linked
to each other to form a ring; R.sub.5 and R.sub.6 are each
independent C1-C7 alkyl or C2-C7 alkenyl; and R.sub.7 and R.sub.8
are each hydrogen.
14. The bis(aminosilyl)alkylamine compound of claim 13, wherein the
bis(aminosilyl)alkylamine compound represented by Chemical Formula
1 is represented by Chemical Formula 2 or 3: ##STR00029## In
Chemical Formula 2 or 3, R is C1-C7 alkyl or C2-C7 alkenyl; R.sub.5
and R.sub.6 are each independent C1-C7 alkyl or C2-C7 alkenyl; and
R.sub.7 is each hydrogen; R.sub.11 to R.sub.14 are each
independently hydrogen, C1-C5 alkyl, or C2-C5 alkenyl; and n and m
are each independently an integer of 1 to 7.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
The present application is a U.S. National Phase of International
Patent Application Serial No. PCT/KR2018/003655 entitled
"COMPOSITION FOR DEPOSITING SILICON-CONTAINING THIN FILM CONTAINING
BIS(AMINOSILYL)ALKYLAMINE COMPOUND AND METHOD FOR MANUFACTURING
SILICON-CONTAINING THIN FILM USING THE SAME," filed on Mar. 28,
2018. International Patent Application Serial No. PCT/KR2018/003655
claims priority to Korean Patent Application No. 10-2017-0040078
filed on Mar. 29, 2017 and Korean Patent Application No.
10-2017-0055632 filed on Apr. 28, 2017 and Korean Patent
Application No. 10-2018-0035010 filed on Mar. 27, 2018. The entire
contents of each of the above-referenced applications are hereby
incorporated by reference for all purposes.
TECHNICAL FIELD
The present invention relates to a composition for depositing a
silicon-containing thin film and a method for manufacturing a
silicon-containing thin film using the same, and more particularly,
to a composition for depositing a silicon-containing thin film,
containing a specific compound, a bis(aminosilyl)alkylamine
compound as a precursor for depositing a thin film, and a method
for manufacturing a silicon-containing thin film using the
same.
BACKGROUND ART
A silicon-containing thin film is manufactured through various
deposition processes in a semiconductor field to thereby be
manufactured in various forms such as a silicon film, a silicon
oxide film, a silicon nitride film, a silicon carbonitride film,
and a silicon oxynitride film, and an application field of the
silicon-containing thin film may be wide.
Particularly, since the silicon oxide film and the silicon nitride
film have a significantly excellent barrier property and oxidation
resistance, the silicon oxide film and the silicon nitride film are
used as an insulating film, a diffusion barrier, a hard mask, an
etch stop layer, a seed layer, a spacer, a trench isolation, an
intermetallic dielectric material, and a passivation layer in
manufacturing an apparatus.
Recently, a polycrystalline silicon thin film has been used in a
thin film transistor (TFT), a solar cell, and the like, and an
application field thereof has been gradually diversified.
As a representative technology for manufacturing a
silicon-containing thin film known in the art, there are a
metal-organic chemical vapor deposition (MOCVD) method for reacting
a gas-type silicon precursor and a reaction gas with each other to
form a film on a surface of a substrate or directly reacting the
gas-type silicon precursor and the reaction gas with each other on
the surface to form a film and an atomic layer deposition (ALD)
method for physically or chemically adsorbing a gas-type silicon
precursor and sequentially injecting a reaction gas to form a film.
Various technologies for manufacturing a thin film such as a
low-pressure chemical vapor deposition (LPCVD) method applying the
above-mentioned method, a plasma-enhanced chemical vapor deposition
(PECVD) method and a plasma-enhanced atomic layer deposition
(PEALD) method capable of performing deposition at a low
temperature, and the like, are applied to processes for
manufacturing next-generation semiconductors and display devices to
thereby be used to form a ultra-fine pattern and deposit an
ultra-thin film having uniform and excellent properties at a
nano-scale thickness.
Representative examples of a precursor used to form the
silicon-containing thin film may include silane, silane compounds,
aminosilane, and alkoxysilane compounds. Specific examples thereof
may include silane chloride compounds such as dichlorosilane
(SiH.sub.2Cl.sub.2) and hexachlorodisilane (Cl.sub.3SiSiCl.sub.3),
trisilylamine (N(SiH.sub.3).sub.3), bis-diethylaminosilane
(H.sub.2Si(N(CH.sub.2CH.sub.3).sub.2).sub.2),
di-isopropylaminosilane (H.sub.3SiN(i-C.sub.3H.sub.7).sub.2), and
the like. These precursors have been used in mass-production
processes for manufacturing semiconductors and displays.
However, due to fineness of devices caused by ultra-high
integration of the devices and an increase in aspect ratio, and
diversification of materials of the devices, a technology of
forming an ultra-fin thin film having a uniform and thin thickness
and excellent electrical properties at a low temperature to be
desired has been required. Therefore, a high-temperature process
(600.degree. C. or more) using an existing silicon precursor, a
step coverage, etching properties, and physical and electric
properties of the thin film have become problems, such that the
development of a novel more excellent silicon precursor and a
method for forming a thin film have been studied.
Technical Problem
An object of the present invention is to provide a composition for
depositing a silicon-containing thin film, containing a
bis(aminosilyl)alkylamine compound capable of being used as a
precursor of the silicon-containing thin film.
Another object of the present invention is to provide a method for
manufacturing a silicon-containing thin film using the composition
for depositing a silicon-containing thin film according to the
present invention.
Another object of the present invention is to provide a
bis(aminosilyl)alkylamine compound capable of being used as a
precursor of a silicon-containing thin film.
Technical Solution
In one general aspect, there is provided a composition for
depositing a silicon-containing thin film containing: a
bis(aminosilyl)alkylamine compound, which has excellent physical
properties as a precursor for thin film deposition, as a precursor
for silicon-containing thin film deposition, wherein the
bis(aminosilyl)alkylamine compound is represented by the following
Chemical Formula 1.
##STR00001##
(In Chemical Formula 1, R is (C1-C7)alkyl or (C2-C7)alkenyl;
R.sub.1 to R.sub.4 are each independently hydrogen, (C1-C7)alkyl,
or (C2-C7)alkenyl, or R.sub.1 and R.sub.2, and R.sub.3 and R.sub.4
are each independently linked to each other to form a ring; and
R.sub.5 to R.sub.8 are each independently hydrogen, halogen,
(C1-C7)alkyl, or (C2-C7)alkenyl.)
Preferably, in Chemical Formula 1 according to an exemplary
embodiment of the present invention, R.sub.5 to R.sub.7 may be each
independently hydrogen, halogen, (C1-C7)alkyl, or (C2-C7)alkenyl,
and R.sub.8 may be hydrogen.
In order to allow the composition to have excellent properties
suitable for thin film deposition, it is preferable that the
bis(aminosilyl)alkylamine compound according to the exemplary
embodiment of the present invention may be represented by the
following Chemical Formula 2 or 3.
##STR00002##
(In Chemical Formula 2 or 3, R is (C1-C7)alkyl or (C2-C7)alkenyl;
R.sub.5 to R.sub.7 are each independently hydrogen, halogen,
(C1-C7)alkyl, or (C2-C7)alkenyl; R.sub.11 to R.sub.14 are each
independently hydrogen, (C1-C5)alkyl, or (C2-C5)alkenyl; and n and
m are each independently an integer of 1 to 7.)
Preferably, in Chemical Formula 2 or 3 according to the exemplary
embodiment of the present invention, R.sub.5 to R.sub.7 may be each
independently hydrogen or (C1-C5)alkyl; R.sub.11 to R.sub.14 may be
each independently hydrogen, (C1-C5)alkyl, or (C2-C5)alkenyl; and n
and m may be each independently an integer of 1 to 4.
Preferably, the bis(aminosilyl)alkylamine compound represented by
Chemical Formula 1 according to the exemplary embodiment of the
present invention may be represented by the following Chemical
Formula 4 or 5.
##STR00003##
(In Chemical Formulas 4 and 5, R is (C1-C7)alkyl or (C2-C7)alkenyl;
R.sub.11 to R.sub.14 are each independently hydrogen, (C1-C7)alkyl,
or (C2-C7)alkenyl; R.sub.5 and R.sub.6 are each independently
(C1-C7)alkyl, or (C2-C7)alkenyl; and n and m are each independently
an integer of 1 to 7.)
Preferably, in Chemical Formula 4 or 5 according to the exemplary
embodiment of the present invention, R may be (C1-C5)alkyl; R.sub.5
and R.sub.6 may be each independently (C1-C5)alkyl; and n and m may
be each independently an integer of 1 to 4.
Preferably, the bis(aminosilyl)alkylamine compound represented by
Chemical Formula 1 according to the exemplary embodiment of the
present invention may be represented by the following Chemical
Formula 6 or 7.
##STR00004##
(In Chemical Formulas 6 and 7, R is (C1-C7)alkyl or (C2-C7)alkenyl;
R.sub.11 to R.sub.14 are each independently hydrogen, (C1-C7)alkyl,
or (C2-C7)alkenyl; and n and m are each independently an integer of
1 to 7.)
Preferably, in Chemical Formula 6 or 7 according to the exemplary
embodiment of the present invention, R may be (C1-C5)alkyl;
R.sub.11 to R.sub.14 may be each independently hydrogen,
(C1-C5)alkyl, or (C2-C5)alkenyl; and n and m may be each
independently an integer of 1 to 4.
The bis(aminosilyl)alkylamine compound according to the exemplary
embodiment of the present invention may be selected from the
following compounds, but is not limited thereto.
##STR00005## ##STR00006##
In another general aspect, there is provided a method for
manufacturing a silicon-containing thin film using the composition
for depositing a silicon-containing thin film described above.
The composition for depositing a silicon-containing thin film may
be deposited by an atomic layer deposition (ALD) method, a chemical
vapor deposition (CVD) method, a metal-organic chemical vapor
deposition (MOCVD) method, a low-pressure chemical vapor deposition
(LPCVD) method, a plasma-enhanced chemical vapor deposition (PECVD)
method, or a plasma-enhanced atomic layer deposition (PEALD)
method, and the silicon-containing thin film may be a silicon oxide
(SiO.sub.2) film, a silicon oxy carbide (SiOC) film, a silicon
nitride (SiN) film, a silicon oxy nitride (SiON) film, a silicon
carbonitride (SiCN) film, or a silicon carbide (SiC) film.
More specifically, the method for manufacturing a
silicon-containing thin film may include:
a. maintaining a temperature of a substrate mounted in a chamber at
30 to 500.degree. C.;
b. contacting the composition for depositing a silicon-containing
thin film described above with the substrate to adsorb the
composition for depositing a silicon-containing thin film in the
substrate; and
c. injecting a reaction gas into the substrate in which the
composition for depositing a silicon-containing thin film is
adsorbed to form a silicon-containing thin film, wherein the
reaction gas is supplied after being activated by generating plasma
with a plasma power of 50 to 1000 W.
In another general aspect, there is provided a
bis(aminosilyl)alkylamine compound represented by Chemical Formula
1 described above.
In order to more efficiently deposit a high-quality thin film, the
bis(aminosilyl)alkylamine compound represented by Chemical Formula
1 may be represented by Chemical Formula 2 or 3.
Advantageous Effects
A composition for depositing a silicon-containing thin film
contains a bis(aminosilyl)alkylamine compound which is a liquid at
room temperate and has high volatility and excellent thermal
stability as a precursor, such that a high-quality
silicon-containing thin film having a high purity and durability
may be provided under lower plasma power and film formation
temperature conditions.
Further, in a method for manufacturing a silicon-containing thin
film using the composition for depositing a silicon-containing thin
film according to the present invention, excellent thermal
stability and deposition rate, and excellent stress intensity may
be implemented even under a low film formation temperature
condition, and in a silicon-containing thin film manufactured
thereby, contents of impurities such as carbon, oxygen, and
hydrogen are minimized, thereby making it possible to manufacture a
silicon-containing thin film having a high purity, excellent
physical and electrical properties, excellent resistance against
hydrogen fluoride, an excellent water vapor transmission rate, and
an excellent step coverage.
BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 is a view illustrating a result obtained by measuring vapor
pressures of bis(aminosilyl)alkylamine compounds prepared in
Examples 1 and 2.
FIG. 2 is a view illustrating results obtained by performing
thermogravimetric analysis on the bis(aminosilyl)alkylamine
compounds prepared in Examples 1 and 2.
FIG. 3 is a view illustrating results obtained by performing
infrared spectroscopic analysis on deposited films of silicon oxide
thin films manufactured in Examples 3 to 5.
FIG. 4 is a view illustrating results obtained by performing
infrared spectroscopic analysis on deposited films of silicon
nitride thin films manufactured in Examples 6 to 9.
DETAILED DESCRIPTION
Best Mode
The present invention provides a composition for depositing a
silicon-containing thin film containing a bis(aminosilyl)alkylamine
compound, which is a liquid at room temperature and has high
volatility and excellent thermal stability to thereby be used as a
useful precursor for forming a silicon-containing thin film,
wherein the bis(aminosilyl)alkylamine compound is represented by
the following Chemical Formula 1.
##STR00007##
(In Chemical Formula 1, R is (C1-C7)alkyl or (C2-C7)alkenyl;
R.sub.1 to R.sub.4 are each independently hydrogen, (C1-C7)alkyl,
or (C2-C7)alkenyl, or R.sub.1 and R.sub.2, and R.sub.3 and R.sub.4
are each independently linked to each other to form a ring; and
R.sub.5 to R.sub.8 are each independently hydrogen, halogen,
(C1-C7)alkyl, or (C2-C7)alkenyl.)
The composition for depositing a silicon-containing thin film
according to the present invention contains a precursor for
depositing a thin film represented by Chemical Formula 1, such that
film formation may be performed at a low temperature, and at the
same time, a high-quality thin film having high durability may be
easily manufactured.
Further, the composition for depositing a silicon-containing thin
film according to the present invention contains the precursor for
depositing a thin film represented by Chemical Formula 1, the thin
film may be deposited at a high thin film deposition rate, and the
film has excellent stress properties and water vapor transmission
rate.
The reason may be that as the bis(aminosilyl)alkylamine compound
represented by Chemical Formula 1, contained in the composition for
depositing a silicon-containing thin film has two aminosilyl groups
and one alkyl or alkenyl group as substituents, the
bis(aminosilyl)alkylamine compound has high volatility and
excellent thermal stability.
Preferably, in Chemical Formula 1 according to the exemplary
embodiment, R.sub.5 to R.sub.7 may be each independently hydrogen,
halogen, (C1-C7)alkyl, or (C2-C7)alkenyl, and R.sub.8 may be
hydrogen.
Preferably, the bis(aminosilyl)alkylamine compound represented by
Chemical Formula 1 according to an exemplary embodiment of the
present invention may be represented by the following Chemical
Formula 2 or 3.
##STR00008##
(In Chemical Formula 2 or 3, R is (C1-C7)alkyl or (C2-C7)alkenyl;
R.sub.5 to R.sub.7 are each independently hydrogen, halogen,
(C1-C7)alkyl, or (C2-C7)alkenyl; R.sub.11 to R.sub.14 are each
independently hydrogen, (C1-C5)alkyl, or (C2-C5)alkenyl; and n and
m are each independently an integer of 1 to 7.)
In the bis(aminosilyl)alkylamine compound represented by Chemical
Formula 2 or 3 according to the present invention, two aminosilyl
functional groups and one alkyl or alkenyl group are substituted,
such that the bis(aminosilyl)alkylamine compound is thermally
stable, and at the same time, the bis(aminosilyl)alkylamine
compound has a silazane backbone in which at least one hydrogen
atom in at least one of two aminosilyl functional groups is
substituted, such that the bis(aminosilyl)alkylamine compound has
high volatility as a liquid at room temperature. Therefore, the
bis(aminosilyl)alkylamine compound may be significantly usefully
used to form a silicon-containing thin film.
More specifically, the bis(aminosilyl)alkylamine compound according
to the present invention, which is a compound having the silazane
backbone, essentially has two aminosilyl functional groups
##STR00009## and silyl in one of the aminosilyl functional groups
necessarily has a functional group containing at least one hydrogen
atom
##STR00010## such that the bis(aminosilyl)alkylamine compound may
have excellent effects as the precursor for depositing a thin
film.
Preferably, in Chemical Formula 2 or 3 according to the exemplary
embodiment of the present invention, R.sub.5 to R.sub.7 may be each
independently hydrogen or (C1-C5)alkyl; R.sub.11 to R.sub.14 may be
each independently hydrogen, (C1-C5)alkyl, or (C2-C5)alkenyl; and n
and m may be each independently an integer of 1 to 4.
More preferably, the bis(aminosilyl)alkylamine compound represented
by Chemical Formula 1 according to the present invention may be
represented by the following Chemical Formula 4 or 5.
##STR00011##
(In Chemical Formulas 4 and 5, R is (C1-C7)alkyl or (C2-C7)alkenyl;
R.sub.11 to R.sub.14 are each independently hydrogen, (C1-C7)alkyl,
or (C2-C7)alkenyl; and R.sub.5 and R.sub.6 are each independently
(C1-C7)alkyl, or (C2-C7)alkenyl; and n and m are each independently
an integer of 1 to 7.)
Preferably, in Chemical Formulas 4 and 5 according to the exemplary
embodiment of the present invention, R may be (C1-C5)alkyl; R.sub.5
and R.sub.6 may be each independently (C1-C5)alkyl; and n and m may
be each independently an integer of 1 to 4. More preferably, the
bis(aminosilyl)alkylamine compound may be represented by Chemical
Formula 4, and in Chemical Formula 4, R may be (C1-C3)alkyl; and
R.sub.5 and R.sub.6 may be each independently (C1-C3)alkyl.
Preferably, the bis(aminosilyl)alkylamine compound represented by
Chemical Formula 1 according to the exemplary embodiment of the
present invention may be represented by the following Chemical
Formula 6 or 7.
##STR00012##
(In Chemical Formulas 6 and 7, R is (C1-C7)alkyl or (C2-C7)alkenyl;
R.sub.11 to R.sub.14 are each independently hydrogen, (C1-C7)alkyl,
or (C2-C7)alkenyl; and n and m are each independently an integer of
1 to 7.)
More preferably, in Chemical Formulas 6 and 7, R may be
(C1-C5)alkyl; R.sub.11 to R.sub.14 may be each independently
hydrogen, (C1-C5)alkyl, or (C2-C5)alkenyl; n and m may be each
independently an integer of 1 to 4. Preferably, R may be
(C1-C5)alkyl; R.sub.11 to R.sub.14 may be each independently
(C1-C5)alkyl; and n and m may be each independently 1 to 4. More
preferably, the bis(aminosilyl)alkylamine compound may be
represented by Chemical Formula 6, wherein in Chemical Formula 6, R
may be (C1-C3)alkyl; and R.sub.11 to R.sub.14 may be each
independently (C1-C3)alkyl.
When silyl groups of two aminosilyl groups in the silazane backbone
of the bis(aminosilyl)alkylamine compound according to the present
invention have two or four hydrogen atoms, the
bis(aminosilyl)alkylamine compound has more excellent reactivity
and thermal stability as the precursor for depositing a thin film,
such that a higher-quality thin film may be manufactured.
In view of the precursor for depositing a thin film having more
excellent properties, the bis(aminosilyl)alkylamine compound
represented by Chemical Formula 4 according to the exemplary
embodiment of the present invention may be represented by the
following Chemical Formula 4-1.
##STR00013##
(In Chemical Formula 4-1, R is (C1-C7)alkyl or (C2-C7)alkenyl;
R.sub.1 and R.sub.2 are each independently hydrogen, (C1-C7)alkyl,
or (C2-C7)alkenyl, or R.sub.1 and R.sub.2 is each independently
linked to each other to form a ring; and R.sub.5 is (C1-C7)alkyl or
(C2-C7)alkenyl.)
In view of the precursor for depositing a thin film having more
excellent properties, the bis(aminosilyl)alkylamine compound
represented by Chemical Formula 6 according to the exemplary
embodiment of the present invention may be represented by the
following Chemical Formula 6-1.
##STR00014##
(In Chemical Formula 6-1, R is (C1-C7)alkyl or (C2-C7)alkenyl; and
R.sub.1 and R.sub.2 are each independently (C1-C7)alkyl, or
(C2-C7)alkenyl, or are linked to each other to form a ring.)
Although not limited, but a specific example of the
bis(aminosilyl)alkylamine compound represented by Chemical Formula
1 according to the exemplary embodiment of the present invention
may include the following compounds.
##STR00015## ##STR00016##
The composition for depositing a silicon-containing thin film
according to the present invention needs to necessarily contain the
bis(aminosilyl)alkylamine compound represented by Chemical Formula
1 as the precursor for depositing a thin film, and the
bis(aminosilyl)alkylamine compound may be contained in the
composition for depositing a silicon-containing thin film in a
content range in which the content may be recognized by those
skilled in the art in consideration of film formation conditions, a
thickness, properties, or the like of the thin film.
As used herein, the term "alkyl" means linear, branched, and cyclic
saturated and unsaturated hydrocarbons having 1 to 7 carbon atoms,
preferably, 1 to 5 carbon atoms, and more preferably 1 to 3 carbon
atoms, and examples thereof may include methyl, ethyl, propyl,
isopropyl, butyl, isobutyl, neobutyl, pentyl, and the like.
As used herein, the term "halogen" means a halogen element, and
examples thereof include fluoro, chloro, bromo, and iodo.
As used herein, the term "alkenyl" as a single group or a part of
another group means a straight-chain, branched-chain, or cyclic
hydrocarbon radical having 2 to 7 carbon atoms and one or more
carbon-carbon double bonds. A more preferable alkenyl radical is a
lower alkenyl radical having 2 to 5 carbon atoms. The most
preferable lower alkenyl radical is a lower alkenyl radical having
about 2 to 3 carbon atoms. Further, the alkenyl group may be
substituted at a random usable attachment point. Examples of the
alkenyl radical include ethenyl, propenyl, allyl, butenyl, and
4-methylbutenyl. The terms "alkenyl" and "lower alkenyl" include
radicals having cis and trans orientations or alternatively, E and
Z orientations.
As used herein, the phrase "R.sub.1 and R.sub.2, and R.sub.3 and
R.sub.4 are each independently linked to each other to form a ring"
includes the case in which R.sub.1 and R.sub.2 are linked to each
other to form a ring but R.sub.3 and R.sub.4 do not form a ring;
the case in which on the contrary, R.sub.1 and R.sub.2 do not form
a ring but R.sub.3 and R.sub.4 are linked to each other to form a
ring; and the case in which R.sub.1 and R.sub.2 are linked to each
other to form a ring and R.sub.3 and R.sub.4 are linked to each
other to form a ring, wherein the formed ring may be an alicyclic
or aromatic ring containing N, and preferably, an alicyclic
ring.
As used herein, the term "alicyclic ring" means a compound that is
not an aromatic compound among organic compounds having a cyclic
bonding structure.
The bis(aminosilyl)alkylamine compound represented by Chemical
Formula 1 according to the present invention may be prepared using
a method as long as the method may be recognized by those skilled
in the art.
In addition, the present invention provides a method for
manufacturing a silicon-containing thin film using the composition
for depositing a silicon-containing thin film according to the
present invention.
Since in the method for manufacturing a silicon-containing thin
film, the composition for depositing a silicon-containing thin film
according to the present invention, containing the
bis(aminosilyl)alkylamine compound represented by Chemical Formula
1, which is a liquid art room temperature and normal pressure and
has high volatility and excellent thermal stability, as the
precursor is used, the handling may be easy, it is possible to
manufacture various thin films, and it is possible to manufacture a
silicon-containing thin film having a high purity, an excellent
water vapor transmission rate, and excellent thin film stress
properties at a high deposition rate even at a low temperature and
a low power.
The silicon-containing thin film manufactured by the method
according to the present invention has excellent durability and
electric properties, and resistance against hydrogen fluoride and
step coverage thereof are also excellent.
In the method for manufacturing a silicon-containing thin film
according to the present invention, the silicon-containing thin
film may be formed by any method as long as it may be recognized by
those skilled in the art. However, preferably, the
silicon-containing thin film may be formed by an atomic layer
deposition (ALD) method, a chemical vapor deposition (CVD) method,
a metal-organic chemical vapor deposition (MOCVD) method, a
low-pressure chemical vapor deposition (LPCVD) method, a plasma
enhanced chemical vapor deposition (PECVD) method, or a plasma
enhanced atomic layer deposition (PEALD) method, but PECVD, ALD, or
PEALD is more preferable in order to allow the thin film to be more
easily deposited, and allow the manufactured thin film to have
excellent properties.
The silicon-containing thin film according to the present invention
may be a silicon oxide (SiO.sub.2) film, a silicon oxy carbide
(SiOC) film, a silicon nitride (SiN) film, a silicon oxy nitride
(SiON) film, a silicon carbonitride (SiCN) film, or a silicon
carbide (SiC) film, and various thin films having high quality,
particularly, a thin film usable as an encapsulant of an organic
light emitting diode (OLED), may be manufactured.
More specifically, the method for manufacturing a
silicon-containing thin film according to the present invention may
include:
a. maintaining a temperature of a substrate mounted in a chamber at
30 to 500.degree. C.;
b. contacting the composition for depositing a silicon-containing
thin film according to the present invention with the substrate to
adsorb the composition for depositing a silicon-containing thin
film in the substrate; and
c. injecting a reaction gas into the substrate in which the
composition for depositing a silicon-containing thin film is
adsorbed to form a silicon-containing thin film.
More specifically, the method for manufacturing a
silicon-containing thin film according to the present invention may
include:
a. maintaining a temperature of a substrate mounted in a chamber at
30 to 500.degree. C.;
b. contacting the composition for depositing a silicon-containing
thin film according to the present invention with the substrate to
adsorb the composition for depositing a silicon-containing thin
film in the substrate;
c. purging the remaining composition for depositing a
silicon-containing thin film and by-products;
d. injecting a reaction gas into the substrate in which the
composition for depositing a silicon-containing thin film is
adsorbed to form a silicon-containing thin film; and
e. purging the remaining reaction gas and by-products, wherein the
reaction gas in step D) may remove a ligand of the
bis(aminosilyl)alkylamine compound contained in the composition for
depositing a silicon-containing thin film to form a Si--O atomic
layer.
Preferably, the reaction gas according to the exemplary embodiment
of the present invention may be supplied after being activated by
generating plasma at a plasma power of 50 to 1000 W.
In the method for manufacturing a silicon-containing thin film
according to the exemplary embodiment of the present invention, a
bis(aminosilyl)alkylamine compound according to the present
invention is used as the precursor, such that the reaction gas may
be activated at preferably 30 to 500.degree. C., and more
preferably 30 to 300.degree. C. by generating plasma at a low
plasma power of 50 to 1000 W, preferably 100 to 800 W, and more
preferably 400 to 600 W, thereby making it possible to manufacture
the thin film.
In the method for manufacturing a silicon-containing thin film
according to the exemplary embodiment of the present invention,
deposition conditions may be adjusted depending on a structure or
thermal properties of a desired thin film. Examples of the
deposition condition according to the exemplary embodiment of the
present invention may include an injection flow rate of the
composition for depositing a silicon-containing thin film
containing the bis(aminosilyl)alkyl amine compound, injection flow
rates of the reaction gas and a carrier gas, pressure, RF power,
the temperature of the substrate, and the like. As non-restrictive
examples of the deposition conditions, the injection flow rate of
the composition for depositing a silicon-containing thin film may
be adjusted in a range of 10 to 1000 cc/min, the injection flow
rate of the carrier gas may be adjusted in a range of 10 to 1000
cc/min, the injection flow rate of the reaction gas may be adjusted
in a range of 1 to 1500 cc/min, the pressure may be adjusted in a
range of 0.5 to 10 torr, the RF power may be adjusted in a range of
50 to 1000 W, and the temperature of the substrate may be adjusted
in a range of 30 to 500.degree. C., preferably 80 to 300.degree.
C., but the deposition conditions are not limited thereto.
The reaction gas used in the method for manufacturing a
silicon-containing thin film according to the present invention is
not limited, but may be one selected from hydrogen (H.sub.2),
hydrazine (N.sub.2H.sub.4), ozone (O.sub.3), oxygen (O.sub.2),
nitrous oxide (N.sub.2O) ammonia (NH.sub.3), nitrogen (N.sub.2),
silane (SiH.sub.4), borane (BH.sub.3), diborane (B.sub.2H.sub.6),
and phosphine (PH.sub.3), or a mixed gas of one or more thereof,
and the carrier gas may be one selected from nitrogen (N.sub.2),
argon (Ar), and helium (He), or a mixed gas of two or more
thereof.
The substrate used in the method for manufacturing a
silicon-containing thin film according to the present invention may
be a substrate containing one or more semiconductor materials
selected from Si, Ge, SiGe, GaP, GaAs, SiC, SiGeC, InAs, and InP; a
silicon-on-insulator (SOI) substrate; a quartz substrate; a glass
substrate for a display; or a flexible plastic substrate made of
polyimide, polyethylene terephthalate (PET), polyethylene
naphthalate (PEN), polymethylmethacrylate (PMMA), polycarbonate
(PC), polyethersulfone (PES), polyester, and the like, but is not
limited thereto.
Further, the silicon-containing thin film may be directly formed on
the substrate. Alternatively, a large number of conductive layers,
dielectric layers, insulating layers, or the like, may also be
formed between the substrate and the silicon-containing thin
film.
In addition, the present invention provides a bis(aminosilyl)alkyl
amine compound capable of being used as a precursor of a
silicon-containing thin film. The bis(aminosilyl)alkyl amine
compound according to the present invention is represented by the
following Chemical Formula 1.
##STR00017##
(In Chemical Formula 1, R is (C1-C7)alkyl or (C2-C7)alkenyl; and
R.sub.1 to R.sub.4 are each independently hydrogen, (C1-C7)alkyl,
or (C2-C7)alkenyl, or R.sub.1 and R.sub.2, and R.sub.3 and R.sub.4
are each independently linked to each other to form a ring; and
R.sub.5 to R.sub.8 are each independently hydrogen, halogen,
(C1-C7)alkyl, or (C2-C7)alkenyl.)
The bis(aminosilyl)alkyl amine compound according to the present
invention, represented by Chemical Formula 1 is a liquid at room
temperature and has high volatility and excellent thermal stability
as described above, such that the bis(aminosilyl)alkyl amine
compound is used as a significantly useful precursor in forming a
silicon-containing thin film.
Further, since in silyl (silicon) of each aminosilyl group, four
hydrogen atoms are present, the bis(aminosilyl)alkyl amine compound
has excellent reactivity, such that the thin film may be deposited
at a rapid deposition rate, and the thin film with a high purity
may be manufactured.
Preferably, the bis(aminosilyl)alkyl amine compound represented by
Chemical Formula 1 may be represented by Chemical Formula 2, and
more preferably Chemical Formula 6 or 7.
The present invention will be described in detail with reference to
the following Examples. The terms and words used in the present
specification and claims should not be interpreted as being limited
to typical meanings or dictionary definitions, but should be
interpreted as having meanings and concepts relevant to the
technical scope of the present invention based on the rule
according to which an inventor can appropriately define the concept
of the term to describe most appropriately the best method he or
she knows for carrying out the present invention.
Therefore, configurations described in the embodiments and shown in
the drawings of the present specification indicate only the most
preferred example rather than indicating all the technical ideas of
the present invention and therefore, it is to be understood that
various equivalents and modifications that can replace the above
configurations may be present.
Further, in all the following Examples, deposition was performed by
a plasma enhanced atomic layer deposition (PEALD) method known in
the art using a commercialized 200 mm single wafer shower head type
ALD apparatus (CN1, Atomic Premium). In addition, deposition was
performed by a plasma enhanced chemical vapor deposition (PECVD)
method known in the art using a commercialized 200 mm single wafer
shower head type CVD (PECVD) apparatus (CN1, Atomic Premium).
A thickness of a deposited silicon-containing thin film was
measured using an ellipsometer (OPTI-PROBE 2600, THERMA-WAVE), and
properties of the thin film were analyzed using infrared
spectroscopy (IFS66V/S & Hyperion 3000, Bruker Optics), X-ray
photoelectron spectroscopy, a water vapor transmission rate (WVTR)
analyzer (MOCON, Aquatran 2), and a stress analyzer (Frontier
Semiconductor, FSM500TC).
[Example 1] Preparation of
Bis(methyldimethylaminosilyl)methylamine
##STR00018##
Under an anhydrous and inert atmosphere, after putting
dichloromethylsilane (SiH(CH.sub.3)Cl.sub.2, 115 g (1.0 mol)) and
n-pentane (577 g (8 mol)) into a 1000 mL flame-dried flask and
slowly adding methylamine (CH.sub.3NH.sub.2, 59 g (1.9 mol))
thereto while maintaining a temperature at -25.degree. C., the
mixture was stirred for 3 hours, and methylamine hydrochloride
((CH.sub.3)NH.sub.3Cl) was removed by filtration. While stirring a
recovered bis(chloromethylsilyl)methylamine
((SiH(CH.sub.3)C1).sub.2N(CH.sub.3)) solution with n-pentane and
maintaining a temperature at -25.degree. C., dimethylamine
((CH.sub.3).sub.2NH, 94 g (7.13 mol)) was slowly added thereto.
After the addition was completed, the reaction solution was slowly
heated to room temperature and stirred at room temperature for 6
hours. After removing dimethylamine hydrochloride
((CH.sub.3).sub.2NH.sub.2Cl, white) formed by filtering the
resultant, a filtrate was obtained. A solvent was removed from this
filtrate under reduced pressure, followed by distillation under
reduced pressure, thereby obtaining
bis(methyldimethylaminosilyl)methylamine
((CH.sub.3).sub.2NSiH(CH.sub.3)).sub.2N(CH.sub.3), 71 g (0.35 mol),
yield: 70%).
.sup.1H-NMR (inCDCl.sub.3): .delta. 0.16 (t, 6H
(Si--CH.sub.3).sub.2), 2.42 (d, 3H (NCH.sub.3)), 2.48 (s, 12H,
((CH.sub.3).sub.2NSi)).sub.2, 4.39 (m, 2H, (--SiHN).sub.2).
[Example 2] Preparation of
Bis(ethylmethylaminosilyl)methylamine
##STR00019##
Under an anhydrous and inert atmosphere, after putting
dichlorosilane (SiH.sub.2Cl.sub.2, 360 g (3.56 mol)) and n-pentane
(3,202 g (27.79 mol)) into a 5000 mL flame-dried Sus reactor (a
high-pressure reactor) and slowly adding methylamine
(CH.sub.3NH.sub.2, 210 g (6.77 mol)) thereto while maintaining a
temperature at -25.degree. C., the mixture was stirred for 3 hours,
and methylamine hydrochloride ((CH.sub.3)NH.sub.3C1)) was removed
by filtration. While stirring a recovered bischlorolsilylamine
((SiH.sub.2C1).sub.2N(CH.sub.3)) solution with n-pentane and
maintaining a temperature at -25.degree. C., ethylmethylamine
((CH.sub.3CH.sub.2)(CH.sub.3)NH), 421 g (7.13 mol)) was slowly
added thereto. After the addition was completed, the reaction
solution was slowly heated to room temperature and stirred at room
temperature for 6 hours. After removing ethylmethylamine
hydrochloride ((CH.sub.3CH.sub.2)(CH.sub.3)NH.sub.2Cl), white)
formed by filtering the resultant, a filtrate was obtained. A
solvent was removed from this filtrate under reduced pressure,
followed by distillation under reduced pressure, thereby obtaining
bis(ethylmethylaminosilyl)methylamine
((CH.sub.3CH.sub.2)(CH.sub.3)NSiH.sub.2).sub.2N(CH.sub.3), 219 g
(1.07 mol), yield: 60%).
.sup.1H-NMR (inC6D6): .delta. 0.97 (t, 6H
(N--CH.sub.2--CH.sub.3).sub.2), 2.47 (s, 6H (Si--NCH.sub.3).sub.2),
2.53 (s, 3H (SiH.sub.2--NCH.sub.3)), 2.81 (q, 4H
(N--CH.sub.2--CH.sub.3).sub.2, 4.77 (m, 4H,
(--SiH.sub.2N).sub.2).
[Example 3] Manufacturing of Silicon Oxide Thin Film by PEALD Using
Bis(ethylmethylaminosilyl)methylamine
Film was formed using the bis(ethylmethylaminosilyl)methyl amine
compound prepared in Example 2 according to the present invention
as a composition for forming a silicon oxide film in a general
plasma enhanced atomic layer deposition (PEALD) apparatus using a
plasma enhanced atomic layer deposition (PEALD) method known in the
art.
As a reaction gas, nitrous oxide was used together with plasma, and
nitrogen corresponding to an inert gas was used for purging. The
film was formed at reaction gas and plasma time of 0.5 seconds. A
specific method for depositing a silicon oxide thin film was
illustrated in Table 1.
A result obtained by analyzing the manufactured silicon oxide thin
film was illustrated in Table 2, and a result obtained by analyzing
the deposited film using infrared spectroscopy was illustrated in
FIG. 3.
[Examples 4 and 5] Manufacturing of Silicon Oxide Thin Film by
PEALD Using Bis(ethylmethylaminosilyl)methylamine
Silicon oxide thin films were manufactured in the same manner as in
Example 3 except for changing deposition conditions illustrated in
the following Table 1 in Example 3, results obtained by analyzing
the manufactured silicon oxide thin film were illustrated in the
following Table 2, and results obtained by analyzing the deposited
film using the infrared spectroscopy were illustrated in FIG.
3.
TABLE-US-00001 TABLE 1 Deposition Conditions of Silicon Oxide Thin
Film by PEALD Reaction Gas Reaction No. of Temperature Precursor
Purge and Plasma Gas Purge Deposition of Substrate Heating
Injection Flow Rate Time Flow Rate RF Time Time Flow Rate Process
(.degree. C.) Temperature (.degree. C.) Time (sec) (sccm) (sec)
(sccm) Power (W) (sec) (sec) (sccm) Cycle Time (sec) Example 3 90
65 0.1 600 0.4 800 400 0.5 0.1 300 614 675 Example 4 90 65 0.1 600
0.4 800 400 0.7 0.1 300 603 784 Example 5 90 65 0.1 600 0.4 800 400
0.9 0.1 300 603 905
TABLE-US-00002 TABLE 2 Evaluation of Properties of Silicon Oxide
Thin Film O/Si Deposition Thickness of Refractive Composition Rate
Thin Film Index Ratio Stress of Film WVTR (.ANG./cycle) (.ANG.) --
-- (MPa) (g/[m.sup.2-day]) Example 3 1.14 700 1.46 1.72 -201
3.2E-02 Example 4 1.16 700 1.47 1.72 -231 1.5E-02 Example 5 1.16
700 1.47 1.72 -275 3.5E-03
[Example 6] Manufacturing of Silicon Nitride Thin Film by PEALD
Using Bis(ethylmethylaminosilyl)methylamine
Film was formed using the bis(ethylmethylaminosilyl)methyl amine
compound prepared in Example 2 according to the present invention
as a composition for forming a silicon nitride film in a general
plasma enhanced atomic layer deposition (PEALD) apparatus using a
plasma enhanced atomic layer deposition (PEALD) method known in the
art. As a reaction gas, nitrogen and ammonia were used together
with plasma as first reaction gas, and nitrogen was used as a
second reaction gas. The nitrogen corresponding to an inert gas was
used for purging. A specific method for depositing a silicon
nitride thin film was illustrated in Table 3.
A specific result obtained by analyzing the silicon nitride thin
film was illustrated in Table 4, and a result obtained by analyzing
the deposited film using an infrared spectrometer were illustrated
in FIG. 4.
[Examples 7 to 9] Manufacturing of Silicon Nitride Thin Film by
PEALD Using Bis(ethylmethylaminosilyl)methylamine
Silicon nitride thin films were manufactured in the same manner as
in Example 6 except for changing conditions illustrated in the
following Table 3 in Example 6, results obtained by analyzing the
manufactured silicon oxide thin film were illustrated in the
following Table 4, and results obtained by analyzing the deposited
film using the infrared spectrometer were illustrated in FIG.
4.
TABLE-US-00003 TABLE 3 Deposition Conditions of Silicon Nitride
Thin Film by PEALD Temper- Reaction Gas Reaction Gas ature
Precursor Purge and Plasma Purge No. of of Sub- Heating Flow Flow
RF Flow RF Flow De- Process strate Tempera- Injection Rate Time
Rate Power Time Rate Power Time Time - Rate position Time (.degree.
C.) ture (.degree. C.) Time (sec) (sccm) (sec) (sccm) (W) (sec)
(sccm) (W) (sec) (sec) (sccm) Cycle (- sec) Example 6 300 65 0.4
6000 0.4 2000 100 1.5 6000 600 4 0.4 6000 300 2130 Example 7 300 65
0.4 6000 0.4 2000 200 1.5 6000 600 4 0.4 6000 300 2130 Example 8
300 65 0.4 6000 0.4 2000 400 1.5 6000 600 4 0.4 6000 300 2130
Example 9 300 65 0.4 6000 0.4 2000 800 1.5 6000 600 4 0.4 6000 300
2130
TABLE-US-00004 TABLE 4 Evaluation of Properties of Silicon Nitride
Thin Film Deposition Rate Thickness of Thin Refractive Index N/Si
Composition Stress of Film WVTR Variable (.ANG./cycle) Film (.ANG.)
-- Ratio (MPa) (g/[m.sup.2-day]) Example 6 Plasma 0.29 88 1.93 1.13
-301 6.2E-02 Power of 100 W Example 7 Plasma 0.22 67 1.89 1.16 -350
1.1E-02 Power of 200 W Example 8 Plasma 0.34 103 1.95 1.18 -416
3.5E-03 Power of 400 W Example 9 Plasma 0.38 114 1.80 1.21 -517
5.3E-03 Power of 800 W
* * * * *
References